Механохімія як перспективна методологія зеленої хімії для промислових каталізаторів
In this survey we have assessed how mechanochemistry techniques comply with the aims of Green Chemistry to minimise the use of environmentally damaging reactants and unwanted by-products. In the publications the preparation of vanadium- phosphorus oxides as industrial catalysts for maleic anhydride...
Gespeichert in:
| Datum: | 2021 |
|---|---|
| Hauptverfasser: | , , , |
| Format: | Artikel |
| Sprache: | Englisch |
| Veröffentlicht: |
V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine
2021
|
| Schlagworte: | |
| Online Zugang: | https://kataliz.org.ua/index.php/journal/article/view/1 |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| Назва журналу: | Catalysis and petrochemistry |
| Завантажити файл: |  |
Institution
Catalysis and petrochemistry| _version_ | 1872008964032430080 |
|---|---|
| author | Zazhigalov, V.A. Wieczorek-Ciurowa, K. Sachuk, O.V. Bacherikova, I.V. |
| author_facet | Zazhigalov, V.A. Wieczorek-Ciurowa, K. Sachuk, O.V. Bacherikova, I.V. |
| author_institution_txt_mv | [
{
"author": "V.A. Zazhigalov",
"institution": "Institute for Sorption and Problems of Endoecology, National Academy of Sciences of Ukraine, General Naumov Str., 13, Kyiv-164, 03164, Ukraine"
},
{
"author": "K. Wieczorek-Ciurowa",
"institution": "Faculty of Chemical Engineering and Technology, Cracow University of Technology, Warszawska Str. 24, 31155 Cracow, Poland"
},
{
"author": "O.V. Sachuk",
"institution": "Institute for Sorption and Problems of Endoecology, National Academy of Sciences of Ukraine, General Naumov Str., 13, Kyiv-164, 03164, Ukraine"
},
{
"author": "I.V. Bacherikova",
"institution": "Institute for Sorption and Problems of Endoecology, National Academy of Sciences of Ukraine, General Naumov Str., 13, Kyiv-164, 03164, Ukraine"
}
] |
| author_sort | Zazhigalov, V.A. |
| baseUrl_str | https://kataliz.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2021-12-10T12:33:52Z |
| description | In this survey we have assessed how mechanochemistry techniques comply with the aims of Green Chemistry to minimise the use of environmentally damaging reactants and unwanted by-products. In the publications the preparation of vanadium- phosphorus oxides as industrial catalysts for maleic anhydride production from n-butane and perspective catalysts of phthalic anhydride manufacture by direct n-pentane oxidation were analyzed. It is shown that mechanochemical activation and synthesis reduces the amount of harmful waste used in the production of the catalyst and increases its effectiveness. Improvement of a catalyst’s properties, help limit production of harmful emissions such as carbon oxides and hydrocarbons. It was established that mechanochemical treatment can by successfully used in the process of industrial vanadium-phosphorus oxide catalysts modification or in the process of introduction in its composition of additives which lead to increase of activity and selectivity of hydrocarbons oxidation. The possibility of the mechanochemistry use in the vanadium-titanium oxide catalysts preparation which are the base catalysts in industrial phthalic anhydride production from o-xylene was determined. It was established that mechanochemical treatment of the vanadium and titanium oxides mixture permits to delete the nitrogen oxides emission in atmosphere and prepared catalysts demonstrate the same phthalic anhydride yield but at low reraction temperature. Catalysts, manufactured by mechanochemical treatment (on the base of molybdenum oxide), provide new techniques for producing compounds as exemplified by the direct oxidation of benzene to form phenol which can replace industrial two-step process from cumene or proposed process of benzene oxidation by N2O. Mechanochemistry treatment could produce catalysts which eliminated the need to use highly toxic nitrogen oxides as reducing agents. The article describes activating Cu-Ce-O catalysts which reduce the temperature of the process for removing carbon monoxide from exhaust gases and as a method for purifying hydrogen u sed in fuel cells. Finally, there is a description of mechanochemically treated catalysts, containing metals and supported on stainless steel supports which are used to remove aromatic hydrocarbons from water sewers. |
| doi_str_mv | 10.15407/kataliz2021.31.001 |
| first_indexed | 2026-03-12T15:49:48Z |
| format | Article |
| fulltext |
Каталіз та нафтохімія, 2021, №31 1
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
Mechanochemistry as advanced methodology in green chemistry for applied
catalysis
V.A. Zazhigalov1, K. Wieczorek-Ciurowa2 , O.V. Sachuk1, I.V. Bacherikova1
1Institute for Sorption and Problems of Endoecology, National Academy of Sciences of Ukraine, General Naumov Str., 13, Kyiv-164, 03164,
Ukraine, vazazh@ukr.net
2Faculty of Chemical Engineering and Technology, Cracow University of Technology, Warszawska Str. 24, 31155 Cracow, Poland,
kwc@ok.edu.pl
In this survey we have assessed how mechanochemistry techniques comply with the aims of Green Chemistry to minimise
the use of environmentally damaging reactants and unwanted by-products. In the publications the preparation of vanadium-
phosphorus oxides as industrial catalysts for maleic anhydride production from n-butane and perspective catalysts of phthalic
anhydride manufacture by direct n-pentane oxidation were analyzed. It is shown that mechanochemical activation and synthesis
reduces the amount of harmful waste used in the production of the catalyst and increases its effectiveness. Improvement of a
catalyst’s properties, help limit production of harmful emissions such as carbon oxides and hydrocarbons. It was established that
mechanochemical treatment can by successfully used in the process of industrial vanadium-phosphorus oxide catalysts
modification or in the process of introduction in its composition of additives which lead to increase of activity and selectivity of
hydrocarbons oxidation. The possibility of the mechanochemistry use in the vanadium-titanium oxide catalysts preparation which
are the base catalysts in industrial phthalic anhydride production from o-xylene was determined. It was established that
mechanochemical treatment of the vanadium and titanium oxides mixture permits to delete the nitrogen oxides emission in
atmosphere and prepared catalysts demonstrate the same phthalic anhydride yield but at low reraction temperature. Catalysts,
manufactured by mechanochemical treatment (on the base of molybdenum oxide), provide new techniques for producing
compounds as exemplified by the direct oxidation of benzene to form phenol which can replace industrial two-step process from
cumene or proposed process of benzene oxidation by N2O. Mechanochemistry treatment could produce catalysts which
eliminated the need to use highly toxic nitrogen oxides as reducing agents. The article describes activating Cu-Ce-O catalysts
which reduce the temperature of the process for removing carbon monoxide from exhaust gases and as a method for purifying
hydrogen u sed in fuel cells. Finally, there is a description of mechanochemically treated catalysts, containing metals and
supported on stainless steel supports which are used to remove aromatic hydrocarbons from water sewers.
Keywords: green chemistry, catalysis, oxide catalysts, mechanochemistry
______________________________________________________________________________________________________
Introduction
Catalysis is crucially important to the economies of the
developed world as shown by the following data. The cost of
catalyst manufacture in the USA in 1992 for the fuel and
chemical industry was estimated to be US$ 1.5 billion dollars
compare this with value of the products manufactured using
catalysts which is approximately 600 times greater (US$ 890
billion dollars) [1]. The cost of production of catalysts in 1995
was $US 8.6 billion rising to $US 11.4 billion by 2001 and
$US 16.2 billion by 2011 with one third of the money being
spent on manufacturing catalysts used for environmental
protection [2-3].
There are a large number of publications [e.g. 3-17]
describing ecological problems where catalyst design could
provide a solution. Developing new catalysts which minimise
damage to the environment falls into the following categories:
1. Reducing toxic by-products (waste). Manufacturing
catalysts using new techniques which reduce the quantity of
damaging by-products.
2. Increasing the yield whilst reducing the number of
harmful by-products. Improving catalyst designs in order to
increasing its efficiency and reducing the number of harmful
by-products/waste.
3. Creating new efficient ecological catalysts.
4.Developing processes that produce the required product
from non-toxic components and without toxic or harmful
waste.
In this survey we present the results from a some of the
work performed that extend the role of catalysts in the field of
environmental protection.
Modern techniques for preparing catalysts include
reactions carried out:
i) in solution using organic and inorganic solvents,
oxidants, stabilisers:
- by impregnation,
- deposition-precipitation,
- sol-gel method,
- ion exchange,
ii) in gas phase:
- grafting,
- CVD,
- PVD,
UDC 544.1
https://doi.org/10.15407/kataliz2021.31.001
mailto:vazazh@ukr.net
mailto:kwc@ok.edu.pl
2 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
- combustion,
iii) in solid state by high-temperature process.
It is important to stress that all the methods generate
significant quantities of liquid and gaseous waste including
harmful/hazardous substances that, according to the Kyoto
protocol, require additional processing to purify regenerate
and reuse solvents [18-23]. Studies of existing data related to
catalytic processes indicate there is much that can be
improved [24–31].
Conventional methods for synthesizing catalysts
including all the methods of optimisation don’t always lead to
increased efficiency. For these reasons it is important to
explore new techniques and solutions in the field of catalyst
technology [32–44] when trying to find solutions to
environmental problems.
An alternative “Green Process” is mechanochemical
treatment [45], which significantly reduces the quantity of
solvent used. It also allows metals and their oxides to be used
in reactions instead of salts. With these changes it is possible
to completely eliminate gaseous waste (COx, NOx, and SO2)
as well as increasing activity and selectivity of the catalyst.
A study into the possible applications of
mechanochemical methods in catalysis is partly presented in
papers [46–49]. Papers [50-52] deal with the synthesis and
modification of solids.
Mechanochemical treatments have the following
variants:
1) Mechanochemical activation of the reactants before
conducting a traditional synthesis – MChA
2) Mechanochemical activation of the catalyst prepared in
the traditional way (including doping) – MChA
3) Mechanochemical synthesis of catalyst by high energy
reactive milling – MChS
4) Mechanocatalytic process as a result of mechanical
treatment - MChCP
The following sections provide explanations and
examples of all the techniques mentioned above, together with
reasons as to why they should be considered as “Green
Chemistries”.
Experimental
Catalyst preparation and characterization methods
Mechanochemical treatment was provided using two
different high-energy laboratory planetary mills:
1. Pulverissette 6 (by Fritsch GmbH) with vial and ball
made of Si3N4 and WC with a rotation speed 550-600 rpm.
2. A mill with vial and balls of hardened steel with
rotation speed of 3,000 rpm. The mass proportions of balls to
sample were 10:1 and 10-20:1, respectively. The milling
processes were performed in air and liquid media (water or
ethanol).
The phase identification and physico-chemical
characteristics of milling products were determined using the
following methods:
• X-ray powder diffraction (XRD) patterns were
recorded on a Philips X’Pert or Philips PW 1830
diffractometers (CuK).
• The binding energy was determined using X-ray
photoelectron spectroscopy (XPS) with a VG scientific
ESCA-3 X-ray photoelectron spectrometer (Al K1.2).
The binding energies were referenced to the C 1s line
(284.8 eV) determination.
• Specific surface area (BET) of samples was
determined using thermal method of nitrogen adsorption
(Gazochrom-2).
• Morphology of the surface was pictured using a
scanning electron microscope (SEM) Hitachi S-4000.
• Micro-Raman spectra were obtained by Dilor Labram
spectrometer (He Ne laser – 632.8nm). The spectrometer
was connected to the electron microscope to analyse the
surface.
• The composition of catalysts surface was investigated
using atomic force microscopy (AFM) with Nanoscope
E Digital Instruments Scanning Probe Microscope
Controller.
Catalytic oxidation processes of practical importance
used for testing the reactivity of mechanochemically prepared
metal oxide catalysts:
▪ partial oxidation of n-butane (1.6 vol. % in air) in
apparatus with a flow reactor of stainless steel, described
in detail [53];
▪ partial oxidation of o-xylene (0.9 vol. % in air) in
analogous conditions;
▪ selective reduction of NO (900 pm) by ammonia
(1000 ppm) with He containing 1 vol. % of O2);
▪ partial oxidation of benzene (1.1 vol. % in air) in a
quartz flow reactor;
▪ CO oxidation (1 vol. %) in combination with O2 (1
vol. %) in He in a flow reactor of stainless steel.
A mixture of gases in the measurements of
temperature-programmed catalytic reaction (TPR) was used:
CO (1 vol. %), H2 (75 vol. %), O2 (1 vol. %), He (23 vol. %).
A quartz flow reactor with product analysis using quadruple
mass-spectrometer was used.
The concentration of hydrocarbons in water after their
oxidation during mechanochemical treatment was measured
by chromato-mass spectrometry (Varian 3400 with Incos 50
Finnigan).
Results and Discussion
1.Vanadium-phosphorus oxide catalysts
The industrial process for manufacturing maleic
anhydride is based on the oxidation of n-butane in the
presence of vanadium-phosphorus oxide (VPO) catalysts
different compositions but the base of these catalysts is the
composition which contents vanadium and phosphorus oxides
with atomic ratio V/P near to 1. [54-58]. The different nature
additives to this composition which increase the activity and
selectivity of the catalysts can be introduced in different steps
of the catalyst synthesis. The most used method of VPO
catalysts preparation based on reaction between V2O5 and
H3PO4 in organic media (most used is butanol) with an
addition of the reducing agent in this composition (most used
is benzyl alcohol or oxalic acid). The molar ratio butanol/V2O5
in the synthesis is 6-9 and reducing agent to V2O5 is equal to
1/1-2 [54-59]. The addition of reducing agent in reaction
Каталіз та нафтохімія, 2021, № 31 3
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
mixture connected with low rate of the catalyst precursor
VOHPO4·0.5H2O formation in the presence of butanol only.
The big quantity of butanol used in the synthesis determines
the necessity its reuse in this process. In same time partial
oxidation of the butanol in synthesis process to aldehydes and
acids affects in negative way the crystal structure of the
precursor. So, the purification of the solvent becomes an
essential step prior to its use in formation of VOHPO4·0.5H2O
in order to reduce the amount of the aldehydes and acids in
solvent. It was noted that the using oxalic and benzyl alcohol
partially reduces V5+ to V4+ ions which speeds up the reaction
of VOHPO4·0.5H2O formation but even with these
enhancements the process still takes 12 -18 hours to complete.
1.1 Mechanochemical activation of reactants (MChA)
It is necessary to note that early we found that
mechanochemical activation of V2O5 changes its morphology
and undergoes a partial reduction to produce V4+ ions. Refer to
Table 1 and papers [59-62] for details.
The obtained results permit to predicted that the use of
the V2O5 after its mechanochemical treatment in
VOHPO4·0.5H2O preparation can permit to excluded the
participation of reducing agent in the synthesis. The properties
of the VPO catalysts prepared on the base of V2O5-MChA
without reducing agent in n-butane oxidation to maleic
anhydride presented in Table 2. The obtained results show that
synthesized catalysts are not inferior the catalyst prepared by
traditional method but demonstrate higher activity and
selectivity. Further improvements, to the catalyst, were made
by milling V2O5 in ethanol and water.
Таble 1. Properties of V2O5 after mechanochemical treatment under different conditions
V2O5
sample
Medium/time,
min
BET,
m2/g
XRD,
I010/I110
XPS data
BE V 2p3/2, eV V4+/V5+ ratio
I Initial sample 4.1 1.1 517.8 - 0.0
A Air/30 19.2 0.8 517.7 516.4 0.10
E-1 Ethanol/20 8.0 4.1 517.9 516.5 0.13
E-2 Ethanol/30 8.2 4.2 517.6 516.1 0.37
W-1 Water/20 27.0 2.1 517.8 516.4 0.04
W-2 Water/30 1.6 * 517.6 516.2 0.41
* VO2 reflexes were only observed
Table 2. Properties of VPO catalysts synthesized with V2O5-MChA
Initial V2O5
sample
VPO synthesized catalysts
BET,
m2/g
XRD,
I001/I220
BE , eV
V 2p3/2
n-Butane oxidation*
XC4, % SMA, % CCOx,vol. % CC4ex,vol. %
Traditional synthesis
I 20.2 1.05 517.5 74 62 1.80 0.42
Synthesis without reducing agent
A 21.4 1.07 517.6 70 62 1.70 0.48
E-1 30.2 1.92 517.4 85 78 1.20 0.24
E-2 14.1 1.32 517.5 81 76 1.24 0.30
W-1 24.6 1.47 517.4 81 78 1.14 0.30
W-2 17.5 0.96 517.3 77 68 1.58 0.37
Modified synthesis
E-1 28.6 1.88 517.5 83 80 1.06 0.27
E-2 18.5 1.54 517.4 82 77 1.21 0.29
W-1 24.0 1.56 517.5 82 80 1.05 0.29
* XC4 – n-butane conversion, SMA – selectivity to maleic anhydride, CCOx – CO and CO2 concentration in exhaust gases, CC4ex – n-butane
concentration in exhaust gases.
4 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
а b
Fig.1. The samples of VPO catalysts prepared by traditional (a) and modified (b) methods.
In the same it was established that the use of V2O5-
MChA as raw material in VOHPO4·0.5H2O preparation leads
to a decrease of time this synthesis up to 2-4 h that is lower
than in traditional method (see above). This fact permits to
proposed the decrease of solvent quantity in synthesis of
VOHPO4·0.5H2O at V2O5-MChA using. The results obtained
at С4Н9ОН/V2O5 = 2.0-2.5 (three times less than traditional
method) presented in Table 2 (modified synthesis) and show
that prepared samples have better properties in n-butane
oxidation than the catalyst prepared in traditional conditions.
A possible explanation for this increased activity is the
formation of thin crystal plates (See Figure 1) which are
predominantly vanadyl (VO2+) plane which correspond to
those found in mechanochemically pre-treated V2O5 (Table
1). The presence of V4+ ions in the initial oxide increases the
formation of the precursor phase and because the time taken
for the synthesis is reduced the crystals don’t thicken in the
(001) plane.
When looked at from the environmental perspective,
this technique has some significant benefits:
- When producing the VPO catalysts the use of
mechanochemical pre-treatment of V2O5 removes the need to
add reducing agents oxalic and benzyl alcohol.
- During production of the catalyst less solvent is
needed (reduce the ratio of n-butanol to V2O5 from 1:6-9 to
1:2.0-2.5) and fewer toxic by-products are produced.
- The resulting catalyst has greater selectivity and
activity which reduces the quantity of un-reacted n-butane.
- The catalyst synthesized on the base of V2O5-MChA
reduces the quantity of carbon oxides (CO and COx) in the
maleic anhydride production.
1.2 Mechanochemical activation of the catalyst
obtained in a traditional way
The first data about mechanochemical activation
(MChA) of VPO catalysts prepared by traditional method
were reported in Patents [63, 64]. In our publications [65-67]
the influence of medium nature on VPO precursor MChA at
treatment in high power mill (3000 rpm) was studied and it
was shown that treatment in ethanol permits to an increase the
catalysts activity and selectivity. The precursor treatment in
water less influenced on its catalyst properties but MChA of
the sample in air increases the catalyst activity only. These
results were confirmed by the data published later [68].
In this paper the results obtained at VPO precursor
treatment in less energetic mill (600 rpm) in ethanol media are
presented. It was established that the MChA of the precursor
prepared by traditional technique leads to an increase this
properties in n-butane oxidation to maleic anhydride (Table
3).
In same time the quantity of COx and un-reacted n-
butane as environmental harmful pollutants essential
decreases. The sum of the COx emission in environment (with
addition of necessity of un-reacted butane oxidation)
decreases up to 1.4 vol. %.
The study showed that the improvements of the sample
properties in the oxidation of n-butane are attributable to the
formation of nano-dispersion areas of the active phase
adjacent to amorphous vanadium phosphate (See Figure 2).
So, the mechanochemical activation of the catalyst
precursor gives the following improvements: i) an increase of
the catalyst properties in partial n-butane oxidation; ii) a
decrease the quantity of COx produced as a by product; iii) a
reduce the quantity of un-reacted n-butane.
1.3 Mechanochemical synthesis of the doped VPO
catalysts
This section describes the benefits that accrue from
mechanochemical synthesis of VPO catalysts containing
additive elements. Well known that industrial VPO catalysts
contain the additives of different transition metals with atomic
ratio Me:V between 0.05–0.10 : 1 [53-58]. The most effective
metals to use for this purpose are cobalt and bismuth [53, 55,
58, 69-73], which are introduced into the synthesis process of
the VPO pre-cursor in the form of salts (CoCl2·6H2O and
Bi(NO3)3·5H2O).
Каталіз та нафтохімія, 2021, № 31 5
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
Таble 3. Properties of VPO catalysts after mechanochemical treatment of precursor
Time of MChA,
min
XRD,
I001/I220
BE, eV n-Butane oxidation*
V 2p3/2 P 2p1/2 XC4, % SMA, % CCOx,vol. % CC4ex,vol. %
- 1.05 517.5 133.9 74 62 1.80 0.42
30 1.22 517.4 133.8 77 68 1.58 0.37
60 1.47 517.4 133.7 83 73 1.43 0.27
120 1.63 517.3 133.8 84 79 1.13 0.26
240 1.92 517.3 133.7 83 81 1.01 0.27
480 ** 517.4 133.8 79 74 1.31 0.34
* symbols are analogous to Table 2.
** sample contains amorphous phase
Table 4. Properties of VPO catalysts doped by Co and Bi
Catalyst Method of preparation n-Butane oxidation
XC4, % SMA, % CCOx,vol. % CC4ex,vol. %
VPO Traditional 74 62 1.80 0.42
VPO-Co Traditional 85 62 2.07 0.24
VPO-Co MChS-Water 87 64 2.00 0.21
VPO-Co MChS-Ethanol 84 75 1.34 0.26
VPO-Bi Traditional 76 68 1.56 0.38
VPO-Bi MChS-Water 85 69 1.69 0.24
VPO-Bi MChS-Ethanol 88 74 1.46 0.19
As result for every ton of catalyst synthesised in this way,
40kg of HCl and 80kg of NO2 are produced as by-products.
We have explored the possibility of adding these
elements by mechanochemical treatment of the VPO
precursor with cobalt and bismuth oxides in water and
ethanol. In papers [53, 73] we describe what happens to the
bismuth and cobalt salts during the traditional process for
synthesis VPO catalyst. The bismuth salt forms a BiPO4 phase
in the VPO structure and the cobalt salt disperses uniformly
without forming a separate phase. The results obtained in
process of MChS by treatment of the VPO precursor + Bi2O3
and VPO precursor + Co2O3 mixtures presented in Figure 3.
These data show the increased dispersion of bismuth and
cobalt salts that occur during mechanochemical synthesis
compared with the traditional method.
The data of the Table 4 presented a comparison of the
activity of the catalysts produced under different conditions.
The study shows that mechanochemical synthesis of VPO
catalysts, doped by additive elements, improves the oxidation
of n-butane in comparison with doped samples prepared by
traditional method. This improvement is accompanied by a
reduction of COx in exhaust gases which formed as a by-
product in maleic anhydride production. Taken together with
the fact that mechanochemical preparation of the doped
catalysts eliminate the production of harmful by-products HCl
and NO2, this procedure certainly qualifies as a “Green
Chemistry”.
In summary the presented results show that in the
production of effective VPO catalysts n-butane oxidation to
maleic anhydride by mechanochemical methods are the more
environmentally acceptable for the following reasons:
• Reduce the volume of organic solvent (n-butanol)
used in the catalyst manufacture process by 66%;
• Eliminate the addition of reducing agents (oxalic and
benzyl alcohol) in catalyst production;
• Decrease the waste associated with solvent
purification;
• Eliminate the formation of by-products HCl and NO2
in synthesis of the catalyst;
• Reduce COx emission in maleic anhydride
manufacture from n-butane on 8,000 tons per year for every
15,000 tons of maleic acid manufactured in a unite industrial
reactor.
Fig. 2. The structure of the sample after 240 min of
MChA.
6 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
а б с
Fig. 3. The distribution of Me (white) in base VPO composition: Me = Bi (a, b) or Co (c). Traditional synthesis (a), MChS
(b, c). SEM in BSE mode.
Table 5. Properties of V2O5 (10 %) and TiO2 mixture after mechanochemical treatment
MChA treatment conditions XRD, I010/I110
(V2O5)
XPS data
B.E., eV Ratio V/Ti
Medium Time, min Ti 2 p V 2p
- - 3.1 459.2 517.7 0.76
Water 10 3.0 459.2 517.6 1.11
Water 30 3.2 459.3 517.8 1.17
Water 60 3.1 459.1 517.7 1.28
Ethanol 10 5.3 459.1 517.6 1.05
Ethanol 30 4.7 459.3 517.6 0.56
Ethanol 60 4.5 459.1 517.7 0.51
Ethanol* 10 15.3 459.2 517.6 0.85
* melted V2O5 with I010/I110 = 30 was used
2.Vanadium-titanium oxide catalysts
Сatalysts based on vanadia (V2O5) and titania (TiO2)
are used in the industrial production of phthalic anhydride
from ο-xylene [74-76] and selective reduction of nitrogen
oxides [10, 77-79]. The most active catalysts used in the
production of phthalic anhydride are TiO2 with 7-15% of the
surface comprised of V2O5 and additional chemical elements.
The catalyst is synthesized from aqueous NH4VO3 and
produces NOx (0.06 t per 1 t of the catalyst) in the preparation
process. We conducted a study to find whether it was possible
to produce vanadium-titanium-oxide catalysts by
mechanochemical treatment of V2O5 and TiO2 in different
milling media. Previous study of the properties of the V2O5
and TiO2 mixture subjected to mechanochemical treatment is
described in papers [80-82]. Paper [82] describes the activity
of the synthesized samples on the oxidation of toluene. These
studies were shown the possibility of vanadium oxide
dispersion on titania surface and its supporting on titanium
oxide.
The data of the Table 5 show how the
mechanochemical treatment affected the dispersal of V2O5 in
the mixture with TiO2 [83]. The breakdown of vanadium
oxide in water does not change the morphology of the
particles and partial dissolution to form “polyvanadia acids”
with next their supporting accompanied by an increases the
ratio of vanadium to titanium of the surface layer.
Mechanochemical treatment in ethanol results in isotropic
disintegration of vanadium oxide (as shown by the XRD data)
and after 10 minutes of milling the proportion of V2O5 to TiO2
on the surface is increased as shown by the XPS data (Table
5). Increasing the treatment time leads to a sharp decline in the
V2O5/ TiO2 ratio. This may be attributable to supporting of
excess titanium oxide on the previously formed surface of the
sample.
This explanation is supported by the study of the
samples using a micro-Raman spectroscopy method (See
Figure 4). Supporting of V2O5 after mechanochemical
treatment in water is uniform as shown by the nearly identical
spectra for point A and B on the surface area (Fragment 1).
Secondary coating by TiO2 (treatment in ethanol) is non
uniform (seen as island structures with sharp edges) as shown
by differences in the spectra for points A and B (See Figure 4,
Fragment 2). In the case of ‘melted’ V2O5 (most oriented to
vanadyl plane 010) coating of the
TiO2 takes place instantly (due to the high resistance of
melted V2O5 (Table 5).
2.1 Partial oxidation of o-xylene
The catalytic properties of V2O5/TiO2 samples
prepared by mechanochemical synthesis in the partial
oxidation of о-xylene are given in Table 6. The obtained
Каталіз та нафтохімія, 2021, № 31 7
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
results were compared with the patent data [84] and data of
the study of the industrial catalyst ‘XS’R-1211/2.
The difference in activity between samples obtained by
mechanochemical treatment in ethanol and water can be
explained by the following observation. V2O5 is dispersed less
evenly and forms islands on the TiO2 surface when ethanol is
used. These islands reduce the likelihood that oxygen will
diffuse from neighboring vanadium atoms the consequent
oxidation of the product to form carbon oxides.
The data presented in Table 6 show that the catalysts,
synthesized by mechanochemical treatment of V2O5 and TiO2
in ethanol are active at temperatures of 70-1000 С lower than
that required by the traditional method. In same time these
catalysts demonstrate practically analogous phthalic anhydride
yield that patented or industrial catalysts. It is necessary to
note that exploitation of the industrial catalyst at a temperature
of 400 ºC accompanied its deactivation [74, 75] and
stabilization of the catalyst properties realized by addition of
SO2 to the reaction mixture. The catalyst synthesized by
mechanochemical treatment doesn’t require such a high
reaction temperature and therefore eliminates the need to add
SO2 and its removal from phthalic anhydride manufacture
gases.
To summarize, the mechanochemical synthesis of
V2O5/TiO2 catalysts proposed by us [85]: i) eliminates
nitrogen oxides during catalysts preparation, ii) allows the
reaction to take place at a lower temperature, iii) provide the
same yield of phthalic anhydride as traditional catalysts, iv)
eliminates the need to add and subsequently remove SO2.
А
В
А
В
1 2
А
В
А
В
Fig. 4. Micro-Raman spectra for points A and B of the V2O5/TiO2 samples after MChA in water
(1) and ethanol (2) during 30 min.
8 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
2.2 Selective reduction of NOx
The catalysts produced by mechanochemical treatment
were studied with respect to their ability to remove nitrogen
oxides (Selective Reduction SCR), especially in the outlet
gases. The data in Table 7 shows that catalyst, prepared by
milling in water, is the most effective at removing NOx. It is
assumed that even distribution of V2O5 as monolithic layer on
the surface of
TiO2 is an essential factor in the process which
corresponded to proposed mechanism of the process [86]. The
comparison results obtained on MChS prepared catalysts with
literature data [86] shows that their properties are practically
equivalent to traditional catalysts but their preparation method
eliminate the formation of NOx in this process.
3 Molybdenum oxide catalysts. Direct oxidation of
benzene to phenol by molecular oxygen.
In our investigation [87] it was established that
mechanochemical treatment of MoO3 in ethanol leads to the
formation of Magnelli phase -Mo8O23. It was shown that this
sample demonstrates activity in direct benzene oxidation to
phenol by molecular oxygen. It is well known [23, 24] that
direct oxidation benzene to phenol is preferable to industrial
process on the base of isopropyl benzene (cumene). The
success in this direction was obtained in benzene oxidation by
N2O in the presence of Fe-containing zeolite catalysts (see,
e.g. [88-89]). The drawback of this method is the use of N2O,
which is environmentally harmful and which must be added to
the reaction mixture in excess. So, the direct oxidation of
benzene using molecular oxygen is most promising method
from green chemistry point.
Table 6. Properties of the V2O5/TiO2 catalysts in o-xylene oxidation
Catalyst o-Xylene oxidation*
Tr.,
0C SV, h-1 YPhA, mol. %
MChS, water, 60 min 340 2700 71.6
MChS, ethanol, 30 min 280 3960 78.7
MChS, ethanol, 60 min 300 3960 81.4
MChS, ethanol, 10 min** 280 3960 82.0
US Pat [83] 370 2700 81.2
“XS” R-1211/2 380 3900 81.6
* Tr. – reaction temperature, SV – space velocity, YPhA – yield of phthalic anhydride
** melted V2O5
Table 7. Selective reduction of NO by NH3 on V2O5/TiO2 catalysts*
Catalyst Tr.,
0C SV, h-1 XNO, %
MChS, water, 60 min 340 9000 98
MChS, ethanol, 30 min 380 7000 96
MChS, ethanol, 60 min 380 7000 97
MChS, ethanol, 10 min** 400 7000 95
* Tr. – reaction temperature, SV – space velocity, XNO – NO conversion
** melted V2O5
Table 8. Properties of МоО3/TiO2 samples after mechanochemical treatment in ethanol
Catalyst Time of MChA, min Benzene oxidation*
Tr.,
0C XC6H6, % SPhOH, mol. %
MoO3 50 360 32 8
MoO3/TiO2 (10 %) 50 360 28 12
MoO3/TiO2 (10 %) 180 360 34 5
MoO3/TiO2 (20 %) 30 340 28 11
MoO3/TiO2 (20 %) 60 340 34 16
MoO3/TiO2 (20 %) 120 330 35 17
MoO3/TiO2 (40 %) 60 360 33 9
MoO3/TiO2 (40 %) 120 350 35 7
* Tr. – reaction temperature, XC6H6 – benzene conversion, SPhOH – selectivity to phenol formation
Каталіз та нафтохімія, 2021, № 31 9
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
In [87] it was shown that the addition of TiO2 (10 wt. %) to
MChT MoO3 permits to an increase the selectivity of phenol
formation in benzene oxidation. This result was the base for
the study of mechanochemical treatment influence on the
MoO3/TiO2 mixtures properties realization. Table 8 gives the
composition of the mixtures, mechanochemical conditions
and characteristics of the catalysts. It shows that a mixture
comprised of 20 % TiO2 and 80 % MoO3 produced the
catalyst with the highest activity and greatest selectivity.
Catalyst activity was increased by extending the milling time
from 60 – 120 minutes and decreased by increasing the
proportion of TiO2 in the mixture.
The Figure 5 compares the surface morphology of the
catalysts obtained by MChA using the AFM method. They
show that the MoO3/TiO2 (20 %) mixture, with a 120 minute
treatment time (Fig. 5 c), has a surface with the most peaks
and these are jagged when compared with the surface of the
MoO3/TiO2 (40 %) mixture (Fig. 5 d). The comparison with
catalytic properties of the samples shows the maximal
selectivity to phenol formation observed for MoO3/TiO2 (20
%) with most pointed peaks on surface.
The theoretical model for the reaction mechanism can
be follows. The peaks are where the -Mo8O23 Маgnelli
phase is formed with Mo5+ ions present which fix the oxygen
in the form of O- ions [90 – 93] which then directly oxidise
benzene to phenol. TiO2 is crucial to the process of dispersing
the active MoO3 and the formation of the active sites where
oxidation takes place.
Our work, presented here, gives a possible alternative
process for producing phenol from the direct oxidation of
benzene. The reaction is catalysed by mechanochemically
activated mixture of MoO3/ TiO2 which creates a surface with
a -Mo8O23 Маgnelli phase which presents Mo5+ ions which
fix O-, ions. However more research is needed to fully
understand the mechanism involved but developed catalysts
permit to realize process of phenol production from benzene
without participation of harmful N2O.
4.Oxide catalysts based on copper and cerium
It is known [94-97] that catalysts formed from the
oxides of copper and cerium are suitable for removing CO
from exhaust gases which do not contain the metals nickel,
a b
c d
Fig. 5. Surface morphology (AFM) of the samples: a – MoO3/TiO2 (10 %) – 50 min, b –
MoO3/TiO2 (20 %) – 30 min, c – MoO3/TiO2 (20 %) – 120 min, d – MoO3/TiO2 (40 %) – 60 min.
10 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
palladium and platinum. They are also suitable for purifying
hydrogen, used as a liquid fuel, by removing CO [98-103].
Hydrogen is proposed as a Green Chemistry method
for producing electro-energy in fuel cell. The disadvantage of
these catalysts is that in excess hydrogen is oxidized to water
which decreases its selectivity to CO and subsequent
deactivation.
We have explored how preparation methods and
catalyst mixtures affect the activity of the oxidation of CO
[104, 105]. The material shows that the catalyst with the
greatest activity is a mixture comprised of 25 % CuO and
75 % CeO2. In this communication the influence of
mechanochemical treatment on its properties presented.
Figure 6 shows how mechanochemical activation of the
catalyst increases activity in the oxidation of CO. The catalyst
with the greatest activity was obtained by treatment conducted
in ethanol medium. In observing the activity of the catalyst
with benzene, we were able to show that it was capable of
catalysing the oxidation of other pollutants.
0
20
40
60
80
100
20 40 60 80 100 120 140
TR.,
0
C
X
C
O
,
%
a
4
3
2
1
0
20
40
60
80
100
0 100 200 300 400
TR.,
0
C
X
C
6
H
6
,
%
b
4
3 2 1
Fig. 6. Dependence of CO (a) and C6H6 (b) conversion on Cu-Ce-O catalysts from reaction temperature: 1 – initial,
2 – MChA in water, 3 – dry MChA, 4 – MChA in ethanol.
a b
Fig. 7. Surface morphology (AFM) of Cu-Ce-O samples: a- initial, b – MChA in etnahol.
0
2
4
6
8
10
12
0 50 100 150 200 250
T,
0
C
I,
a
.u
4
3
2
1
a
0
2
4
6
8
10
12
0 50 100 150 200 250
T,
0
C
I,
a
.u
4
3
2
1
b
Fig.8. Termo-programmed reaction mixture H2 (75 %) – CO (1 %) – O2 (1%) – He on traditional Cu-Ce-O catalyst (a) and
after MChA in ethanol (b). Intensity of the masses: 1 – CO, 2 – H2, 3 – CO2, 4 – H2O.
Каталіз та нафтохімія, 2021, № 31 11
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
Table 9. Mechano-catalytic oxidation of hydrocarbons (0.3 wt. %) in water
Catalyst Hydrocarbon concentration after mechanochemical treatment (MChT)
Benzene Toluene Phenol
15 min 60 min 15 min 60 min 15 min 60 min
V2O5 0.004 0.00003 0.001 0.0004 0.004 0.0002
CuO 0.008 0.0005 0.04 0.008 0.003 0.0003
TiO2 0.006 0.0008 0.002 0.001 0.006 0.0004
Ti/SS* 0.0003 traces 0.006 0.0001 0.0003 traces
Ni/SS 0.0001 traces 0.002 traces 0.0001 traces
Mo/SS 0.0001 traces 0.007 0.0002 0.0003 0.0001
*SS – stainless steel
a b
Fig. 9. Surface morphology Ni/SS sample: a – intial, b – after MChT 60 min.
Figure 7 shows the surface morphology of the catalyst
with and without mechanochemical treatment. The gentle hills
observed in initial sample change on pointed peaks with
nanodimensions top and base of these peaks. It is possible to
suppose that the formation of these nanoforms determines an
increase of the catalyst activity. The X-ray photoelectron
spectroscopy (XPS) measurements indicate that the oxidation
state of the elements is unaffected by the mechanochemical
treatment of the mixture. The literature data [106-109]
describes that the formation of nano-sized oxide clusters
significantly increase the catalytic activity of the oxide
catalysts in the oxidation of CO. The mechanochemically
treated Cu-Ce-O catalyst displays the same surface
morphology and this is the likely explanation for its increased
activity.
The results obtained on this catalyst in CO oxidation
predetermine its study in purifying hydrogen. Figure 8
compared the results from thermo-programmed reaction on: i)
traditionally synthesized sample and ii) mechanochemically
treated sample.The curves show the changes in relative mass
intensity (H2 = 2, H2O = 17/18, CO = 28, CO2 = 44). It can be
seen that for the first simple (initial) the temperature of
maximum oxidation CO and the start of H2 oxidation (Figure
8, a) practically have not difference (vertical line). The sample
after MChA (Figure 8, b) demonstrates difference between
temperature of full CO oxidation and beginning of hydrogen
oxidation (∆T = 15 0C). This difference indicates that Cu-Ce-
O after mechanochemical activation is suitable as a means of
eliminating CO from hydrogen fuel.
The results of this study show that mechanochemical
activation has provided the solution to several problems facing
“Green Chemistry”: i) increases the activity of catalysts used
to oxidise CO in Industrial outlet gases, ii) eliminate aromatic
hydrocarbons referred to as VOC, iii) it provides a suitable
method for purifying hydrogen which is used in low
temperature processes related to “fuel cells”.
5. Mechanochemical reactions – “green chemistry” in
water medium
In [60] it was observed the water decomposed and
hydrogen peroxide generation when metal oxides were treated
in water. This fact formed the basis for postulating a
hypothesis that hydrocarbons could be removed from water
during its mechanochemical treatment in the presence of
oxide catalyst. The first data obtained at benzene-water
mechanochemical treatment [110,111] confirmed this
hypothesis. The drawback of oxide catalysts in this process is
connected with their reduction in process and their partial
destruction.
12 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
In result using the low temperature implantation
method, catalysts containing metals deposited onto a stainless
steel support were synthesized [112-115]. The data of Table 9
show that catalysts prepared in this way are highly effective
when it comes to removing aromatic hydrocarbons from
water.
The results obtained from atomic force microscopy
(AFM), show that in the process of mechano-catalytic reaction
there is no significant alteration to the surface of the catalyst
(See Figure 9).
In addition to these studies we have investigated the
decomposition of distilled water in the presence of catalysts
containing metals supported on stainless steel. In these
experiments we recorded the release of molecular hydrogen
which results from this process. This phenomenon is being
investigated as a method for splitting water and releasing
molecular hydrogen as a way of producing fuel.
Research into mechanocatalytic processes in water
provides another route for “Green Chemistry” to follow and
provide possibilities for removing traces of hydrocarbons from
water and alternative methods for producing of fuel.
Conclusions
In this review of our work we have attempted to show
how mechanochemistry techniques contribute to the principle
of “Green Chemistry”.
Our research has centered on the preparation of
catalysts which reduce the quantities of environmentally
damaging materials used and created as by-products in
essential production processes.
Mechanochemical activation and synthesis have
proved themselves to be very effective techniques for
improving the performance of existing catalysts.
Benefits that accrue from this work are:
• Increased activity which increase of the productivity
of desired product,
• Increased selectivity which means reactions are far
more efficient, allowing more conversion to main product and
fewer unwanted by-products,
• The possibility that catalyst could provide a method
for producing a clean source for fuel cell.
Acknowledgements
The financial support of the National Academy of
Science – Programme ” New functional substances and
materials for chemical manufacture” (Project 13/19-21).
References
1.Armor J.N. Global overview of catalysis. United States
of America. Appl. Catal. A: General. 1996. v. 139. No 1-2. pp.
217-228.
2.Gallei E. and Schwab E. (1999) Development of
technical catalysis. Catal. Today. 1999. v. 51, No 3-4. pp. 535-
546.
3.Handbook of industrial catalysts. Fundamental and
applied catalysts. (M.Twigg, M.Spencer – Eds.). N.-Y.,
Dortrecht: Springer. 2011. 482 P. ISBN 978-0-387-49962-8
4.Courty P.R. and Chauvel A. Catalysis, the turntable for
a clean future. Catal. Today. 1996. v. 29, No 1-4. pp. 3-15.
5.Fritz A. and Pitchon V. The current state of research on
automotive lean NOx catalysis. Appl. Catal. B: Environmental.
1997. v. 13, No 1. pp. 1-25.
6.Sheldon R.A. and Downing R.S. Heterogeneous
catalytic transformation for environmentally friendly production.
Appl. Catal. A: General. 1999. v. 189. No 2. pp.163-183.
7.Blaer H.U., Studer M. The role of catalysis for the clean
production of fine chemicals. Appl. Catal. A: General. 1999.
v.189. No 2. pp. 191-204.
8.Tanabe K. and Holderich W.F. Industrial application of
solid acid-base catalysts. Appl. Catal. A: General. 1999. v.
181.No 2. pp. 399-434.
9.Armor J.N. Striving for catalytically green processes in
the 21st century. Appl. Catal. A: General. 1999. v.189. No 2.
pp.153-162.
10.Pajonk G.M. Some catalytic applications of aerogels
for environmental purposes. Catal. Today. 1999. v. 52. No 1. pp.
3-13.
11.Forzatti P. Environmental catalysis for stationary
applications. Catal. Today. 2000. v. 62, No 1. pp. 51-65.
12.Shelef M. and McCabe R.W. Twenty-five years after
introduction of automotive catalysts: what next? Catal. Today.
2000. v. 62. No 1. pp.35-50.
13.Trong On D., Desplantier-Giscard O., Danumah C.
and Kaliaguine S. Perspectives in catalytic applications of
mesostructured materials. Appl. Catal., A: General. 2001. v. 222.
No 1-2. pp. 299-357.
14.Berndt M. and Landri P. An overview about
Engelhard approach to non-standard environmental catalysis.
Catal. Today. 2002. v. 75. No 1-4. pp. 17-22.
15.Centi G., Ciambelli P., Perathoner S. and Russo P.
Environmental catalysis: trends and outlook. Catal. Today. 2002.
v. 75. no 1-4. pp. 3-15.
16.Centi G. and Perathoner S. Catalysis and sustainable
(green) chemistry. Catal. Today. 2003. v. 77, No 4. pp. 287-297.
17.Centi G., Perathoner S. and Rak Z.S. Reduction of
greenhouse gas emissions by catalytic processes. Appl. Catal. B:
Environmental. 2003. v. 41.No 1-2. pp. 143-155.
18. Kyoto Protocol to the United Nations Framework
Convention on Climate Change (UNFCCC). 1997. L.7, Add.1.
Bonn. https://unfccc. int.
19.Kotel’nikov G.R. and Kachalov D.V. The
manufacturing and use of catalysts for petrochemistry. The state
of the art and problems. Kinetics and Catalysis. 2001. v. 42. No 5.
pp. 718-726.
20. Schmidt F. New catalyst preparation technologies –
observed from an industrial viewpoint. Appl. Catal. A: General.
2001. v. 221. No 1-2. pp.15-21.
21.Campanati M., Fornasari G. and Vaccari A.
Fundamental in the preparation of heterogeneous catalysts. Catal.
Today. 2003. v. 77. No4. pp. 299-314.
22.Encyclopedia of Catalysis. (Horvath I.T. – Ed.). N.Y.:
Wiley and Sons. 2003. v. 1-6. 4772 P.
23.Handbook of Heterogeneous Catalysis. (Ertl G.,
Knozinger H., Schuth F. and Wietkamp J. Eds). N.Y.: Wiley-
VCH. 2008. v. 1-8. 4270 P.
Каталіз та нафтохімія, 2021, № 31 13
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
24.Pasquon I. New processes and perspectives in the field
of heterogeneous oxidation catalysis in relation to other methods
of oxidation. Catal. Today. 1987. v. 1. No 3. pp. 297-333.
25.Nojiri N. and Misono M. Recent progress in catalytic
technology in Japan – A supplement. Appl. Catal. A: General.
1993. v. 93, No 2. pp. 103-122.
26.Clavel A., Delmon B. and Holderich W.F. New
catalytic processes developed in Europe during the 1980’s. Appl.
Catal., A: General. 1994. v. 115, No 2. pp. 175-217.
27.Misono M. and Inui T. New catalytic technologies in
Japan. Catal. Today. 1999. v. 51. No 3-4. pp.369-375.
28.Armor J.N. New catalytic technology commercialized
in the USA during the 1990s. Appl. Catal. A: General. 2001. v.
222.No 1-2. pp. 407-426.
29.Glebov L.S., Zakirova A.G., Tret’yakov V.F.,
Burdeinaya T.N. and Akopova G.S. State of the art research of
catalytic conversion of NOx into N2. Petroleum Chem. 2002. v.
42. No 2. pp.143-172.
30.Rossini S. The impact of catalytic materials on fuel
reformulation. Catal. Today. 2003. v. 77, No 4. pp. 467-484.
31.Setoyama T. Acid-base bifunctional catalysis: An
industrial viewpoint. Catal. Today. 2006. v. 116. No 2. pp. 250-
262.
32.Kochloefl K. Present and future trends in industrial
heterogeneous catalysis. Appl. Catal. A: General. 1999. v. 185.
No2. pp. N10-N14.
33.Martino G. (2000) Catalysis for oil refining and
petrochemistry, recent developments and future trends. Stud. Surf.
Sci. Catal. 2000. v.130. pp. 83-103.
34.Somorjai G.A. and McCrea K. Roadmap for catalytic
science in the 21st century: a personal view of building the future
on past and present accomplishments. Appl. Catal. A: General.
2001. v. 222. No 1-2. pp. 3-18.
35.Emig G. and Liauw M.A. New reaction engineering
concepts for selective oxidation reactions. Topics in Catal. 2002.
v.21. No 1-3. pp. 11-24.
36.Liu C.J., Vissokov G.P. and Jang B.W.L. Catalyst
preparation using plasma technologies. Catal. Today. 2002. v. 72.
No 3-4. pp. 173-184.
37.Kamat P.V. and Meisel D. Nanoparticles in advanced
oxidation processes. Curr. Opin. Colloid Interface Sci. 2002. v. 7.
No 5-6. pp.282-287.
38.Tilley T.D. Molecular design and synthesis of
heterogeneous and single-site, supported catalysts. J. Molec.
Catal. A: Chemical. 2002. v.182-183. pp. 17-34.
39.Marcilly C. Present status and future trends in catalysis
for refining and petrochemicals. J. Catal. 2003. v. 216. No 1-2.
pp. 47-62.
40.Kaspar J., Fornasiero P. and Hickey N. Automotive
catalytic converters: current status and some perspectives. Catal.
Today. 2003. v.77. No 4. pp.419-449.
41.Corma A. and Garcia H. Lewis acids: From
conventional homogeneous to green homogeneous and
heterogeneous catalysis. Chem. Rev. 2003. v.103. No 10.
pp.4307-4365.
42.Dautzenberg F. and Angevine P.J. Encouraging
innovation in catalysis. Catal. Today. 2004. v.93-95. pp. 3-16.
43.Camp C.V. The future of the petrochemical industry in
Europe. Catal. Today. 2005. v. 106. No 1-4. pp.15-29.
44.Brazdil J.F. Strategies for the selective catalytic
oxidation of alkanes. Topics Catal. 2006. v.38. No 4. pp. 289-
294.
45.Wieczorek-Ciurowa K., and Gamrat K.
Mechanochemical syntheses as an example of green processes. J.
Therm. Anal. Cal. 2007. v. 88. No 1. pp. 213-217.
46.Shirokov Yu.G. Mechanochemistry in catalysts
technology (Russ.). Ivanovo: Chem. Techn. Univ. Ivanovo. 2005.
350 P.
47.Molchanov V.V. and Buyanov R.A.
Mechanochemistry of catalysts. Russ. Chem. Rev. 2000.v. 69, No
5. pp. 435-450.
48.Molchanov V.V. and Buyanov R.A. Scientific
grounds for the application of mechanochemistry to catalyst
preparation. Kinetics and Catalysis. 2001. v.42. No 3. pp. 366-
374.
49.Zazhigalov V.A., Wieczorek-Ciurowa K.
Mechanochemiczna aktywacja katalizatorów wanadowych.
Krakow: Wydawnictwo PK. 2015. 454 P. ISBN 978-83-7242-
842-4.
50.Avvakumov E., Senna M. and Kosowa N. Soft
mechanochemical synthesis: A basis for new chemical
technologies. Boston: Kluwer Acad. Publ. 2001. 207 P.
51.Baláž P. Mechanochemistry in nanoscience and
minerals engeineering. Berlin: Springer. 2008. 413 P.
52.Baláž P., Achimovicová M., Baláž M., Billik P.,
Cherkezova-Zheleva Z., Manuel Criado J., Delogu R., Dutková
E., Gaffet E., Jose Gotor E., Kumar R., Mitov I., Rojac T., Senna
M., Streleckii A., Wieczorek-Ciurowa K., Hallmarks of
mechanochemistry: from nanoparticles to technology. Chem.
Soc. Rev. 2013. v. 42. No 18. pp. 7571-7637.
53.Zazhigalov V.A., Haber J., Stoch J., Pyatnitskaya A.I.,
Komashko G.A. and Belousov V.M. Properties of cobalt-
promoted (VO)2P2O7 in the oxidation of butane. Appl. Catal. A:
General. 1993. v. 96, No 2. pp.135-150.
54.Zazhigalov V.A (1992) Phosphates of vanadium as
catalysts for partial oxidation of hydrocarbons С4. Catalysis and
Catalysts (Russ). 1992. V. 28. pp.3-19.
55.Vanadyl pyrophosphate catalysts. (Centi G.- Ed.).
Catal. Today. 1993. v.16, No 1. pp. 1-153.
56.Albonetti S., Cavani F., and Trifiro F. (1996) Key
aspects of catalyst design for the selective oxidation of paraffins.
Catal. Rev. Sci. Eng. 1996. v.38. No 4. pp. 413-438
57.Hodnett B.K. Heterogeneous catalytic oxidation:
Fundamental and technological aspects of the selective and total
oxidation of organic compounds. N.-Y.: Wiley and Sons. 2000.
360 P.
58.Centi G., Cavani F. and Trifiro F. Selective oxidation
by heterogeneous catalysis. N.Y.: Kluwer Acad. 2001. 505 P.
59.Zazhigalov V.A., Haber J., Stoch J., Bogutskaya L.V.
and Bacherikova I.V. Mechanochemistry in preparation and
modification of vanadium catalysts. Stud. Surf. Sci. Catal. 1996.
v.101. pp. 1039-1047.
60.Zazhigalov V.A., Haber J., Stoch J., Kharlamov A.I.,
Bacherikova I.V. and Kowal A. Influence of the
14 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
mechanochemical treatment on the reactivity of V-containing
oxide systems. Solid State Ionics. 1997. v. 101-103. pp. 1257-
1262.
61.Zazhigalov V.A., Kharlamov A.I., Bacherikova I.V.,
Komashko G.A., Khalameida S.V., Bogutskaya L.V., Byl’ O.G.,
Stoch J. and Kowal A. Changes in structure and catalytic
properties of V2О5 caused by mechanochemical treatment.
Theor. Experim. Chem. 998. v. 34. No 2. pp. 162-164.
62.Su D.S., Roddatis V., Willinger M., Wienberg G.,
Kitzelmann E., Schlogl R. and Knozinger H. (2001)
Tribochemical modification of the microstructure of V2O5. Catal.
Lett. 2001. v. 74. No 3-4. pp. 169-175.
63.Higgins R. and Hutchings G.Y. Production of maliec
acid and anhydride. USA Pat. 4317777. 1982. Imper. Chem. Ind.
Ltd., IC3 C07D 307/60.
64.Hanson C.B. and Harrison C.R. Production of
catalysts. Europ. Pat. 0098065. 1983. Imper. Chem. Ind. Ltd.,
IC3 B01J 37/00.
65.Zazhigalov V.A., Haber J., Stoch J., Bogutskaya L.V.,
Bacherikova I.V. Mechanochemistry as activation method of the
V-P-O catalysts for n-butane partial oxidation. Appl. Catal. A:
General. 1996. v.135. No 1. pp. 155-161.
66.Haber J., Zazhigalov V.A., Stoch J., Bogutskaya L.V.,
Bacherikova I.V. Mechanochemistry: the activation method of
VPO catalysts for n-butane partial oxidation. Catal. Today. 1997.
v. 33. No 1. pp. 39-47.
67.Zazhigalov V.A. (1997) Non-traditional methods to
prepare and modify VPO catalysts for selective oxidation of C4-
hydrocarbons. In: Proc. C4 chemistry – manufacture and use of
C4-hydrocarbons. Аachen, DGMK, 1997. pp. 315-322.
68.Fait M., Kubias B., Eberle H.J., Estenfelder M.,
Steinike U. and Schneider M. Tribomechanical pretreatment of
vanadium phosphates: structural and catalytic effects. Catal. Lett.
2000. v.68, No 1-2. pp. 13-18.
69.Yamazoe N., Morishige H., Tamaki J. and Miura N.
Role of amorphous phase and its modification in V-P-O catalysts
for maleic anhydride synthesis from butane. Stud. Surf. Sci. Catal.
1992. v. 75. pp. 1979-1982.
70.Ruiz P., Bastians Ph., Caussin L., Reuse R., Daza L.,
Acosta D. and Delmon B. New Aspects of the Cooperation
between Phases in Vanadium Phosphate Catalysts. Catal. Today.
1993. V. 16. No 1. pp. 99-111.
71. Cornaglia L., Carrara C., Petunchi J. and Lombardo E.
The nature of the Cobalt Salt affects the Catalytic Properties of
Promoted VPO. Stud. Surf. Sci. Catal. 2000. v.130. pp. 1727-
1732.
72.Carrara C., Irusta S., Lombardo E., and Cornaglia L.
Study of the Co-VPO interaction in promoted n-butane oxidation
catalysts. Appl. Catal. A: General. 2001. 217. No 1-2. pp.275-
286.
73.Zazhigalov V.A. (2002) Effect of bismuth additives on
the properties of vanadium. -phosphorus oxide catalyst in the
partial oxidation of n-pentane. Kinetics and Catal. 2002. v. 43.
No 4. pp. 514-521.
74.Nikolov V., Klissurski D. and Anastasov A. Phthalic
anhydride from o-xylene catalysis: Science and Engineering.
Catal. Rev. Sci. Eng. 1991. v. 33. No 3-4. pp. 319-374.
75.Dias C.R., Portela M.F. and Bond G.C. Synthesis of
phthalic anhydride: Catalysts, kinetics, and reaction modeling.
Catal. Rev. Sci. Eng. 1997. v. 39. No3. pp. 169-207.
76.Grzybowska-Swierkosz B. Vanadia-titania catalysts
for oxidation of o-xylene and other hydrocarbons. Appl. Catal. A:
General. 1997. V. 157. No 1-2. pp. 263-310.
77.Bosch H. and Janssen F. Catalytic reduction of
nitrogen oxides. A review on the fundamentals and technology.
Catal. Today. 1988. v. 2. No 4. pp. 369-531.
78.Nojiri N., Sakai Y. and Watanabe Y. Two catalytic
technologies much influence on progress in chemical
development in Japan. Catal. Rev. Sci. Eng. 1995. v. 37. No 1.
pp. 145-178.
79.Heck R.M. Catalytic abatement of nitrogen oxides –
stationary applications. Catal. Today. 1999. v. 53. No 4. pp. 519-
523.
80.Sobalik V., Lapina O., Novgorodova O. and Mastikhin
V. Interaction of vanadium with alumina and titanium during
ultra-high intensity at room temperature as evidenced from 51V
NMR Spectra. Appl. Catal. A: General. 1990. v. 63. No 1. pp.
191-195.
81.Lapina O.B., Shubin A.A. and Nosov A.V.
Characterization of V2O5-TiO2 catalysts prepared by milling by
ESR and solid state 1H and 51V VMR. J. Phys. Chem. B. 1999.
v. 103. No 36. pp. 7579-7606.
82.Bulushev D.A., Kiwi-Minsker L. and Renken A.
(2000) Vanadia/titania catalysts for gas phase partial toluene
oxidation. Spectroscopic characterization and transient kinetics
study. Catal. Today. 2000. v. 57, No 3-4. pp. 231-239.
83.Zazhigalov V.A., Kharlamov A.I., Depero L., Marino
A., Bacherikova I.V., Khalameida S.V. and Stoch J. Effect of
mechanochemical modification on the catalytic properties of the
V2O5-TiO2 system. Theor. Experim. Chem. 2000. v. 36, No 1. pp.
98-102.
84.Sato T., Nakanishi Y., Maruyama R. and Suzuki T.
Catalyst for producing phthalic anhydride. US Patent 4481304.
1984. Nippon Shokubai Kagakiu Kogyo Co Ltd. – IC3
B01J27/24.
85.Zazigalow W., Haber J., Stoch J., Charlamow A.I. and
Baczerikowa I.W. (2006) Sposob wytwarzania katalizatora
wanadowo-tytanowego do utleniania o-ksylenu do bezwodnika
ftalowego. PL Patent 192067. 2006. Publ. 31.08.2006. WUP
08/06.
86.Busca G., Lietti L., Ramis G. and Berti F. Chemical
and mechanistic aspects of the selective catalytic reduction of
NOx by ammonia over oxide catalysts: A review. Appl. Catal. B:
Environmental. 1998. v. 18. No 1-2. pp. 1-36.
87.Zazhigalov V.A., Khalameida S.V., Zaitsev Y.P. and
Bacherikova IV. (2001) Direct benzene oxidation to phenol by
molecular oxygen on modified MoO3. 4th World Congr. Oxid.
Catal. Berlin: Dechema e.V. 2001. v. 1. pp. 291-297.
88.Chernyavsky V.S., Pirutko L.V., Uriarte A.K.,
Kharitonov A.S. and Panov G.I. On involvement of radical
oxygen species O- in catalytic oxidation of benzene to phenol by
nitrous oxide. J. Catal. 2007. v. 245. No 2. pp. 466-469.
89.Yuranov I., Bulushev D.A., Renken A. and Kiwi-
Minsker L. Benzene to phenol hydroxylation with N2O over Fe-
Каталіз та нафтохімія, 2021, № 31 15
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
beta and Fe-ZSM-5: Comparison of activity per Fe-site. Appl.
Catal. A: General. 2007. v.319. pp. 128-136.
90.Yang T.J. and Lunsford J.H. The role O- ions in the
oxidative dehydrogenation of ethane over molybdenum oxide
supported on silica gel. J. Catal. 1980. v. 63, No 2. pp.505-509.
91.Che M., Bonneiot L., Louis C. and Kermarec M.
Coordination chemistry involving oxide catalysts. Mater. Chem.
Phys. 1985. v. 13. No 3-4. pp. 201-220.
92.Serafin J.G. and Friend C.M. (1989) Inhibition of C-H
and C-O bond activation by surface oxygen: stabilization of
surface phenoxide in the reaction of phenol on oxygen-
precovered Mo (110). J. Am. Chem. Soc. 1989. v.111. No 12. pp.
4233-4239.
93.Louis C. and Che M. (1991) Activation and properties
of Mo=O bonds in Mo/SiO2 catalysts. Res. Chem. Intermediates.
1991. V.15, No 1. pp. 81-98.
94.Zhang S.M., Huang W.P., Qiu X.H., Li B.Q., Zheng
X.C. and Wu S.H. Comparative study on catalytic properties for
low-temperature CO oxidation of Cu/CeO2 and CuO/CeO2
prepare via solvated metal atom impregnation and conventional
impregnation. Catal. Lett. 2002. v. 80. No 1-2. pp.41-46.
95.Jung C.R., Han J., Nam S.W., Lim T.H., Hong S.A.
and Lee H.I. Selective oxidation of CO over CuO-CeO2 catalyst:
effect of calcinations temperature. Catal. Today. 2004. v. 93-95.
pp. 183-190
96.Avgouropoulos G. and Ioannidis T. Effect of synthesis
parameters on catalytic properties of CuO-CeO2. Appl. Catal. B:
Environmental. 2006. v. 67. No 1-2. pp. 1-11.
97.Martinez-Arias A., Gamarra D., Fernandez-Garcia M.,
Wang X.Q., Hanson J.C. and Rodriguez J.A. Comparative study
of redox properties of nanosized CeO2 and CuO/CeO2 under
CO/O2. J. Catal. 2006. v.240. No 1. pp. 1-7.
98.Avgouropoulos G., Ioannides T., Matralis H.K.,
Batista J. and Hocevar S. CuO-CeO2 mixed catalysts for selective
oxidation of carbon monoxide in excess hydrogen. Catal. Lett.
2001. v. 73. No 1. pp. 33-40.
99.Kim D.H. and Cha J.E. A CuO-CeO2 mixed oxide
catalyst for CO clean-up by selective oxidation in hydrogen-rich
mixtures. Catal. Lett. 2003. v. 86. No 1-3. pp.107-112.
100.Liu Y., Fu Q. and Stephanopoulos M.F. Preferential
oxidation of CO in H2 over CuO-CeO2 catalysts. Catal. Today.
2004. v.93-95. pp. 241-246.
101.Papvasiliou J., Avgouropoulos G. and Ioannidis T. In
situ combustion synthsis of structured Cu-Ce-O and Cu-Mn-O
catalysts for the production and purification of hydrogen. Appl.
Catal. B: Environmental. 2006. v. 66. No 3-4. pp. 168-174.
102.Ko E.Y., Park E.D., Seo K.W., Lee H.C., Lee D. and
Kim S. A comparative study of catalysts for the preferential CO
oxidation in excess hydrogen. Catal. Today. 2006. v. 116. No 3.
pp. 377-383.
103.Luo M.F., Ma J.M., Lu J.Q., Song Y.P. and Wang
Y.J. High-surface area CuO-CeO2 catalysts prepared by a
surfactant-templated method for low-temperature CO oxidation.
J. Catal. 2007. v. 246. No 1. pp. 52-59.
104.Zazhigalov V., Stoch J., Kowal A., Mikolajczyk M.,
Kirillov S. and Romanova I. Aktywnosc katalizatorow Cu-Ce-O
w utlenianiu tlenku wegla. - 37th Ogolnopolskie Kolokwium
katalityczne. 2005. Krakow: ICSC PAN. pp. 154-155.
105.Romanova I.V., Farbun I.A., Khajnakov S.A.,
Kirillov S.A. and Zazhigalov V.A. (2008) Investigation of
catalytic properties of materials on base of transition metals and
cerium oxides. Reports of National Acad. Sci Ukraine. 2008. No
6. pp. 115-120.
106.Golunski S. and Rajara R. Catalysis at lower
temperature. CATTECH. 2002. v.6. No 1. pp. 30-38.
107.Lin H.K., Chiu H.C., Tsai H.C., Chien S.H. and
Wang C.B. Sythesis, characterization and catalytic oxidation of
carbon monoxide over cobalt oxide. Catal. Lett. 2003. v. 88. No
3-4. pp. 169-174.
108.Taylor S.H., Hutchings G.J. and Mirzaci A.M. The
preparation and activity of copper zinc oxide catalysts for ambient
temperature carbon monoxide oxidation. - Catal. Today. 2003. v.
84. No 3-4. pp. 113-119.
109.Li P., Miser D.E., Rabiei S., Yadav R.T. and
Hajaligol M.R. The removal of carbon monoxide by iron oxide
nanoparticles. Appl. Catal. B: Environmental. 2003. v. 43. No 2.
pp. 151-162.
110.Zazhigalov V.A., Kharlamov A.I. New reaction:
Catalytic selective oxidation of benzene with water oxygen at
mechanochemical treatment of HC/H2O emulsion. – EuropaCat-
3. Krakow: ICSC. 1997. pp. 654-655.
111.Zazhigalov V.A., Khalameida S.V., Litvin N.S.,
Gasior M., Vartikyan L. and Wieczorek-Ciurowa K.
Mechanochemistry and mechano-catalytic processes in
environmental protection. Catalysis: Fundamentals and
Application. III Int. Conf., Novosibirsk: BIC SB RAS. 2007. v. 2.
pp. 583-584.
112.Zazhigalov V.O., Honcharov V.V. The formation of
nanoscale coating on the 12Cr18Ni10Ti steel during ion
implantation. Metallofizika i Noveishie Tekhnologii. 2014. v. 36.
No 6. pp. 757-766.
113.Cherny, A.A., Maschenko, S.V., Honcharov, V.V.,
Zazhigalov, V.A. Nanodimension layers on stainless steel surface
synthesized by ionic implantation and their simulation. Springer
Proceedings in Physics. 2015. v.167. pp. 203-213.
114.Honcharov V., Zazhigalov V., Sawlowicz Z., Socha
R., Gurgol J. Structural, catalytic, and thermal properties of
stainless steel with nanoscale metal surface layer. Springer
Proceedings in Physics. 2017. v.195. pp. 355-364.
115.Zazhigalov V.A., Honcharov V.V., Bacherikova I.V.,
Socha R., Gurgu J. Formation of Nanodimensional Layer of
Catalytically Active Metals on Stainless Steel Surface by Ionic
Implantation. Theor. Experim. Chem. 2018. v. 54 No 2. pp. 128-
137.
Надійшла до редакції 16.04.21 р.
.
16 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
Механохімія як перспективна методологія зеленої хімії для промислових
каталізаторів
В.О. Зажигалов 1, K. Вечорек-Цюрова2 , O.В. Сачук1, I.В. Бачерикова1
1Інститут сорбції та проблем ендоекології, Національна академія наук України, вул. Генерала. Наумова, 13. Київ-164, 03164,
Україна, vazazh@ukr.net
2Факультет хімічної інженерії та технології, Краківський політехнічний інститут, вул. Варшавська, 24, 31155, Краків, Польща,
kwc@ok.edu.pl
В даному огляді показано, як механохімічна обробка може бути включена до технологій зеленої хіміі, що
пов’язано з зниженням використання небезпечних вихідних речовин та утворення супутних продуктів. В роботі
проаналізовано приготування оксидних ванадій фосфорних каталізаторів, які використовують в промисловому процесі
одержання малеїнового ангідриду з н-бутану та розглядають перспективність їх використання в реакції одержання
фталевого ангідриду з н-пентану. Показано, що механохімічна активація вихідних реагентів для синтезу каталізаторів
знижує кількість шкідливих речовин в їх виробництві та підвищує їх каталітичні показники. Підвищення селективності
каталізаторів веде до зниження утворення оксидів вуглецю, а підвищення активності – до зменшення кількості
непрореагованої речовини в вихідних газах процессу каталізу. Показано, що механохімічна обробка може бути також
успішно використана для модифікування відомих промислових оксидних ванадій фосфорних каталізаторів, або
введення до їх складу домішок Які підвищують активність та селективність в окисненні вуглеводнів. Розглянуто
можливість використання механохімії до синтезу оксидних ванадій титанових каталізаторів, на яких базується сьогодня
промисловий процес одержання фталевого ангідриду з о-ксилолу. Встановлено, що механохімічна обробка оксидів
ванадію та титану дозволяє виключити викиди оксидів азoту в процесі синтезу каталізатора, синтезовані каталізатори
дозволяють одержати такий самий вихід фталевого ангідриду, що відомі промислові зразки, але при температурі реакції
значно нижчій. Показано, що механохімія дозволяє синтезувати каталізатори для нових процесів, наприклад одержання
фенолу окисненням бензолу молекулярним киснем (в присутності каталізаторів на основі оксиду молібдену). В
результаті, виникає можливість замінити промисловий двостадійний кумольний процес або конкурувати з
пропонуємим процесом окиснення бензолу оксидом азоту N2O. Показано, що механохімічна активація Cu-Ce-O
каталізатора дозволяє знизити температуру окиснення СО в вихідних газах та цей каталізатор може бути використаний
для очищення водню від монооксиду вуглецю для його подальшого використання в паливних комірках. Також
продемонстровано, що використання оксидних каталізаторів, краще нанесених на металічні носії, дозволяє реалізувати
механо-каталітичне окиснення ароматичних вуглеводнів в водних стоках.
Ключові слова : зелена хімія, каталіз, оксидні каталізатори, механохімія
|
| id | oai:katalizorgua:article-1 |
| institution | Catalysis and petrochemistry |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-03-12T15:49:48Z |
| publishDate | 2021 |
| publisher | V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | katalizorgua/18/5873eb27701e9231a377ddd1be6b2918.pdf |
| spelling | oai:katalizorgua:article-12021-12-10T12:33:52Z Mechanochemistry as advanced methodology in green chemistry for applied catalysis Механохімія як перспективна методологія зеленої хімії для промислових каталізаторів Zazhigalov, V.A. Wieczorek-Ciurowa, K. Sachuk, O.V. Bacherikova, I.V. green chemistry catalysis oxide catalysts mechanochemistry зелена хімія каталіз оксидні каталізатори механохімія In this survey we have assessed how mechanochemistry techniques comply with the aims of Green Chemistry to minimise the use of environmentally damaging reactants and unwanted by-products. In the publications the preparation of vanadium- phosphorus oxides as industrial catalysts for maleic anhydride production from n-butane and perspective catalysts of phthalic anhydride manufacture by direct n-pentane oxidation were analyzed. It is shown that mechanochemical activation and synthesis reduces the amount of harmful waste used in the production of the catalyst and increases its effectiveness. Improvement of a catalyst’s properties, help limit production of harmful emissions such as carbon oxides and hydrocarbons. It was established that mechanochemical treatment can by successfully used in the process of industrial vanadium-phosphorus oxide catalysts modification or in the process of introduction in its composition of additives which lead to increase of activity and selectivity of hydrocarbons oxidation. The possibility of the mechanochemistry use in the vanadium-titanium oxide catalysts preparation which are the base catalysts in industrial phthalic anhydride production from o-xylene was determined. It was established that mechanochemical treatment of the vanadium and titanium oxides mixture permits to delete the nitrogen oxides emission in atmosphere and prepared catalysts demonstrate the same phthalic anhydride yield but at low reraction temperature. Catalysts, manufactured by mechanochemical treatment (on the base of molybdenum oxide), provide new techniques for producing compounds as exemplified by the direct oxidation of benzene to form phenol which can replace industrial two-step process from cumene or proposed process of benzene oxidation by N2O. Mechanochemistry treatment could produce catalysts which eliminated the need to use highly toxic nitrogen oxides as reducing agents. The article describes activating Cu-Ce-O catalysts which reduce the temperature of the process for removing carbon monoxide from exhaust gases and as a method for purifying hydrogen u sed in fuel cells. Finally, there is a description of mechanochemically treated catalysts, containing metals and supported on stainless steel supports which are used to remove aromatic hydrocarbons from water sewers. В даному огляді показано, як механохімічна обробка може бути включена до технологій зеленої хіміі, що пов’язано з зниженням використання небезпечних вихідних речовин та утворення супутних продуктів. В роботі проаналізовано приготування оксидних ванадій фосфорних каталізаторів, які використовують в промисловому процесі одержання малеїнового ангідриду з н-бутану та розглядають перспективність їх використання в реакції одержання фталевого ангідриду з н-пентану. Показано, що механохімічна активація вихідних реагентів для синтезу каталізаторів знижує кількість шкідливих речовин в їх виробництві та підвищує їх каталітичні показники. Підвищення селективності каталізаторів веде до зниження утворення оксидів вуглецю, а підвищення активності – до зменшення кількості непрореагованої речовини в вихідних газах процессу каталізу. Показано, що механохімічна обробка може бути також успішно використана для модифікування відомих промислових оксидних ванадій фосфорних каталізаторів, або введення до їх складу домішок Які підвищують активність та селективність в окисненні вуглеводнів. Розглянуто можливість використання механохімії до синтезу оксидних ванадій титанових каталізаторів, на яких базується сьогодня промисловий процес одержання фталевого ангідриду з о-ксилолу. Встановлено, що механохімічна обробка оксидів ванадію та титану дозволяє виключити викиди оксидів азoту в процесі синтезу каталізатора, синтезовані каталізатори дозволяють одержати такий самий вихід фталевого ангідриду, що відомі промислові зразки, але при температурі реакції значно нижчій. Показано, що механохімія дозволяє синтезувати каталізатори для нових процесів, наприклад одержання фенолу окисненням бензолу молекулярним киснем (в присутності каталізаторів на основі оксиду молібдену). В результаті, виникає можливість замінити промисловий двостадійний кумольний процес або конкурувати з пропонуємим процесом окиснення бензолу оксидом азоту N2O. Показано, що механохімічна активація Cu-Ce-O каталізатора дозволяє знизити температуру окиснення СО в вихідних газах та цей каталізатор може бути використаний для очищення водню від монооксиду вуглецю для його подальшого використання в паливних комірках. Також продемонстровано, що використання оксидних каталізаторів, краще нанесених на металічні носії, дозволяє реалізувати механо-каталітичне окиснення ароматичних вуглеводнів в водних стоках. V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2021-10-26 Article Article application/pdf https://kataliz.org.ua/index.php/journal/article/view/1 10.15407/kataliz2021.31.001 Catalysis and petrochemistry; No. 31 (2021): Catalysis and petrochemistry; 1-16 Каталіз та нафтохімія; № 31 (2021): Каталіз та нафтохімія; 1-16 2707-5796 2412-4176 10.15407/kataliz2021.31 en https://kataliz.org.ua/index.php/journal/article/view/1/1 http://creativecommons.org/licenses/by/4.0 |
| spellingShingle | зелена хімія каталіз оксидні каталізатори механохімія Zazhigalov, V.A. Wieczorek-Ciurowa, K. Sachuk, O.V. Bacherikova, I.V. Механохімія як перспективна методологія зеленої хімії для промислових каталізаторів |
| title | Механохімія як перспективна методологія зеленої хімії для промислових каталізаторів |
| title_alt | Mechanochemistry as advanced methodology in green chemistry for applied catalysis |
| title_full | Механохімія як перспективна методологія зеленої хімії для промислових каталізаторів |
| title_fullStr | Механохімія як перспективна методологія зеленої хімії для промислових каталізаторів |
| title_full_unstemmed | Механохімія як перспективна методологія зеленої хімії для промислових каталізаторів |
| title_short | Механохімія як перспективна методологія зеленої хімії для промислових каталізаторів |
| title_sort | механохімія як перспективна методологія зеленої хімії для промислових каталізаторів |
| topic | зелена хімія каталіз оксидні каталізатори механохімія |
| topic_facet | green chemistry catalysis oxide catalysts mechanochemistry зелена хімія каталіз оксидні каталізатори механохімія |
| url | https://kataliz.org.ua/index.php/journal/article/view/1 |
| work_keys_str_mv | AT zazhigalovva mechanochemistryasadvancedmethodologyingreenchemistryforappliedcatalysis AT wieczorekciurowak mechanochemistryasadvancedmethodologyingreenchemistryforappliedcatalysis AT sachukov mechanochemistryasadvancedmethodologyingreenchemistryforappliedcatalysis AT bacherikovaiv mechanochemistryasadvancedmethodologyingreenchemistryforappliedcatalysis AT zazhigalovva mehanohímíââkperspektivnametodologíâzelenoíhímíídlâpromislovihkatalízatorív AT wieczorekciurowak mehanohímíââkperspektivnametodologíâzelenoíhímíídlâpromislovihkatalízatorív AT sachukov mehanohímíââkperspektivnametodologíâzelenoíhímíídlâpromislovihkatalízatorív AT bacherikovaiv mehanohímíââkperspektivnametodologíâzelenoíhímíídlâpromislovihkatalízatorív |